Orange dye and process of making same.



'amin derivative are somewhat less bright than llnirnn Srnrns nrnrtrier.

PAUL JULIUS, OF LUDWIGSHAFEN, GERMANY, ASSIGNOR TO BADISGHE ANILIN &SODA FABRIK, OF SAME PLACE.

ORANGE DYE AND PROCESS-OF MAKING SAME.

SPECIFICATION forming" part of Letters Patent No. 679,172, dated July23, 1901. Application filed April 1, 1901. Serial No. 53,943. (Nospecimens.)

To all whom it may concern.-

Be it known that vI, PAUL JULIUS, a doctor of philosophy and a chemist,a subject of the Emperor ofAustria-Hungary,residing at Lud-Wigshafen-on-the-Rhine in the Kingdom of Bavaria, Germany, have inventednew and useful Improvements in Orange Dyes, of which the following is aspecification.

My invention relates to the production of orange coloring matter on thefiber by means of certain pyrazolone-carboXylic-acid derivatives.

I have found that phenyl-pyrazolone carboxylic acid, the so-calledtartrazinogen, (which can be obtained by saponifying the condensationproduct of phenyl-hydrazin and oxalyl-acetic ester, see W. Wislicenus,Annale'n, Vol. 246, page 321,) combines readily with primulin sulfonicacid which has been diazotized on the fiber, giving rise to an orangetartrazin coloring-matter. In place of phenyl-pyrazolone carboxylic acidanother homologous or analogous derivative thereof can be employed, suchas can be prepared, for example,by condensing ortho or paratolylhydrazin, alpha or beta naphthyl-hydrazin, or para-nitro-phenyl-hydrazin with oXalyl-acetic ester and subsequent saponification ofthe condensation products thus obtained. The shades produced bycombining these pyrazolone products with diazotized primulin sulfonicacid differ but little from one another. Those produced by means of thealpha-naphthylthe others. In the present state of knowledge my newcoloring-matter can be regarded as a mono-azo compound. The procedurefor obtaining these new shades consists in diazotizing primulin snlfonicacid on the fiber of the material to be dyed in the known manner andthen passing the goods thus treated through a solution of thealphyl-pyrazolone carboxylic acid chosen made alkaline by carbonate ofsoda. After leaving the goods in this solution for from ten (10) totwenty (20) minutes they are wrung out, rinsed, and 0therwise treated asrequired.

I give an example of a method for obtaining pyrazolone bodies which canbe used for the purposes of myinvention; but I do not wish to claim thesame.

Example: Heat together at a temperature of about one hundred (100)degrees centigrade, twenty-one (21) parts of the sodium compound ofoXalyl-acetic ester, sixteen (16) parts of ortho-tolyl-hydrazinhydrochlorid, and one hundred (100) parts of Xylene for about one hour.I-Iydrazone formation ap pears to take place at first, and this isfollowed by further condensation. To complete the latter, add about onehundred and fifty (150) parts of water to the mixture, distil off theXylene by blowing in steam, and when no more hydrocarbon passes over addabout eleven (11) parts of calcined soda to the mixture. Keep it boilingfor about half an hour longer by continuing to pass in steam, and thenadd about eleven and a half (11%) parts of caustic-soda solution,(containing about thirty-five per cent. of NaOH.) Heat on theboiling-water bath until the condensation product formed is saponified,filter from any resinous matter formed, cool, and precipitate the orthotolylpyrazolone carboxylic acid from the filtrate by carefullyacidifying it with hydrochloric acid. The ortho-tolyl-pyrazolonecarboXylic acid thus obtained can be purified by recrystallization fromhot dilute alcohol. In a similar manner para-tolyl, alpha, and betanaphthyl, and para-nitro-phenyl-pyrazolone carboxylic acids can beprepared.

The mono-azo coloring-matter which I wish to claim generically and whichcan be obtained by combining diazotized primulin sulfonic acid withphenyl-pyrazolone carboxylic acid or one ofits hereinbefore-mentionedderivatives is difficultly soluble to practically insoluble in coldwater, as it contains but the sulfo group due to the primulinsulfonicacid. On reducing with zinc-dust and common-salt solution primulinsulfonic acid is regenerated. The shades obtained on cotton by meansthereof are orange and are hardly a1 tered by treatment with dilutecarbonate-ofsoda solution or dilute hydrochloric acid. They areexceeding fast to soap and light.

The mono-azo coloring-matter which I desire to claim specifically andwhich can be de-' rived from diazotized primulin sulfonic acid andpara-nitro-phenyl-pyrazolone carboxylic acid is difticultly soluble incold water with an orange color, the solution becoming redder on theaddition of caustic-soda solution. On reduction with zinc-dust andcommon-salt so lution primulin sulfonic acid is regenerated. The shadesobtained on cotton by means thereof are orange and are hardly altered bytreatment with dilute carbonate-of-soda solution or dilute hydrochloricacid. They are also exceedingly fast to soap and to light.

The following example will serve to illustrate the nature of myinvention and a manner of carrying it into practical effect; but myinvention is not confined to the example. The parts are by weight.

Example: Dye one hundred (100) kilograms of cotton with three (33)kilograms of primulin sulfonic acid and diazotize the primulin sulfonicacid on the fiber in the well-known manner. Rinse the material thustreated in cold water and pass it through a hath made up of tenkilograms of para-nitro-phenylpyrazolone carboxylic acid'and asnfficient excess of carbonate of soda in five thousand (5,000) litersof water. Allow the material to remain in this bath for about twentyminutes, rinse, and dry.

Now what I claim is l. The process of producing orange dye on the fiberby combining primulin sulfonic acid which has been diazotized on thefiber with a hereinbefore-defined phenyl-pyrazolone-carboxylic-acidbody,substantially as described.

2. The process of producing orange dye by combining diazotized primulinsulfonic acid with a hereinbefore-definedphenyl-pyrazolonecarboxylic-acid body, substantially as described.

3. The process of producing orange dye by combining diazotized primulinsulfonic acid with para-nitro-phenyl-pyrazolone carboxylic acid,substantially as described.

4. The new mono-azo dye which can be obtained from diazotized primulinsulfonic acid and a hereinbefore-definedphenyl-pyrazolone-carboxylic-acid body, which is difficultl y soluble topractically insoluble in cold water, which on reduction with zinc-dustand common-salt solution yields primulin sulfonic acid, and which whendeveloped on the cotton fiber produces orange shades, which shades arehardly altered on treatment with dilute carbonate-of-soda solution orwith dilute hydrochloric acid and are exceedingly fast to light andsoap, substantially as described.

5. The new mono-azo dye which can be obtained from diazotized primulinsulfonic acid and para-nitro-phenyl-pyrazolone carboxylic acid, which isdifficultlysoluble in cold water with an orange color which solutionbecomes redder on the addition of caustic-soda solution and which onreduction with zinc-dust and common-saltsolntion yields primulinsulfonic acid, and which when developed on the cotton fiber producesorange shades which are hardly altered on treatment with dilutecarbonate-of-soda solution or on treatment with dilute hydrochloric acidand which are exceedingly fast to light and soap, substantially asdescribed.

In testimony whereof I have hereunto set my hand in the presence of twosubscribing witnesses.

PAUL JULIUS.

\Vitnesses:

JOHN L. HEINKE, JACOB ADRIAN.

